Control of distribution of aluminum alkyls and products derived therefrom

ABSTRACT

A PROCESS FOR PRODUCING ALUMINUM TRIALKYLS OF CONTROLLED ALKYL CHAIN LENGTHS IS DISCLOSED. ETHYLENE IS POLYMERIZED TO 1-OLEFINS WHICH ARE SEPARATED INTO 1-OLEFINS OF SELECTED CHAIN LENGTHS. THE SEPARATED 1-OLEFINS ARE REACTED WITH ALUMINUM AND HYDROGEN TO PRODUCE THE ALUMINUM TRIALKYLS WHICH CAN BE SUBSEQUENTLY GROWN WITH ETHYLENE TO INCREASE CHAIN LENGTHS. THE TRIALKYLS CAN THEN BE OXIDIZED AND HYDROLYZED TO PRODUCE PRIMARY ALCOHOLS.

Nov. 21, 1973 J. A. ACCIARRI ET AL CONTROL OF DISTRIBUTION OF ALUMINUM ALKYLS AND PRODUCTS DERIVED THEREFROM Filed Aug. 4, 1969 GROWTH REACTOR ALUMINUM ALKYLS GENERATTON OLEFINS OLEFINS 7 GENERATION FRACTIONATIONI 4 OLEFINS OXIDATION REACTOR JERRY A. ACCIARRI EUGENE F. KENNEDY INVENTORS.

Q BY wan /L United States Patent US. Cl. 260-448 A 14 Claims ABSTRACT OF THE DISCLOSURE A process for producing aluminum trialkyls of controlled alkyl chain lengths is disclosed. Ethylene is po- 15 lymerized to l-olefins which are separated into l-olefins of selected chain lengths. The separated l-olefins are reacted with aluminum and hydrogen to produce the aluminum trialkyls which can be subsequently grown with ethylene to increase chain lengths. The trialkyls can then be oxidized and hydrolyzed to produce primary alcohols.

BACKGROUND OF THE INVENTION (a) Field of the invention This invention relates to preparation of aluminum alkyls. In a more limited aspect, this invention relates to a method of preparing alcohols from aluminum alkyls having a narrower range of carbon atoms in the hydrocarbon portion of the alcohol than the normal Poisson distribution.

(b) Description of prior art In the commercial production of alcohols from aluminum alkyls, aluminum is reacted with aluminum triethyl and hydrogen to produce aluminum diethyl hydride. The aluminum diethyl hydride is alkylated with ethylene to form aluminum triethyl. For each three moles of aluminum triethyl, two are recycled to form more aluminum diethyl hydride and one is sent to a growth reactor for ethylene additions. The growth product will contain alkyl atoms per group. Therefore, the alcohols formed from such aluminum alkyls will have the same carbon atom distribution. The C to C alcohols are particularly useful, and many schemes have been proposed for altering the normal random distribution to yield the chain lengths of the desired size. Most of these methods involve complicated recycle streams and controls as well as lack of flexibility, since they involve reverse displacement and recycle of olefins.

OBJECT OF THE INVENTION It is an object of this invention to provide a simple process for controlling the alkyl chain lengths in production of aluminum alkyls. Another object of this invention is to provide a simple method of producing alcohols of predetermined carbon atoms.

SUMMARY OF THE INVENTION According to this invention, ethylene is converted to long chain l-olefins, the olefins are fractionated into predetermined cuts, selected olefins are then used for alkylating aluminum, at least a portion of the resulting aluminum trialkyls are subjected to growth with additional ethylene, and the aluminum trialkyls are converted to alcohols by oxidation and hydrolysis.

DESCRIPTION OF PREFERRED EMBODIMENTS The process of this invention can best be described by reference to the drawing. Ethylene is fed via conduit 1 to olefin generation Zone 21 where the ethylene is converted to l-olefins under a pressure of 2,000 p.s.i. to 5,000 p.s.i.,

3,775,456 Patented Nov. 27, 1973 a temperature in the range C. to 220 C., and in the presence of 0.5 percent to 10 percent aluminum triethyl. Alternatively, the ethylene can be converted to olefins by growth with aluminum triethyl, the growth product displaced by ethylene forming aluminum triethyl which is recycled for additional growth and l-olefins of random chain lengths. In either case, the olefins from Zone 21 pass via Conduit 2 to olefin fractionation Zone 22. Olefins suitable for sales or of undesired chain lengths are removed via Conduit 4. The olefins to be converted to end product are passed via Conduit 5 to alkylation Zone 23 wherein they are used for alkylating aluminum from Conduit 12 in the presence of hydrogen from Conduit 13 thereby forming aluminum trialkyls. The aluminum trialkyls having alkyls of lower chain lengths than desired are passed via Conduits 6 and 8 to growth reaction Zone 24 where additional ethylene from Conduit 14 is introduced onto the alkyl groups. Those aluminum alkyls of the desired chain length are passed from Zone 23 via Conduits 6 and 7 to oxidation Zone 25. The growth product from Zone 24 is passed via Conduit 9 to oxidation Zone 25 via Conduit 9. Oxygen is fed to Zone 25 via Conduit 15 forming aluminum trialkoxide. The alkoxides from Zone 25 pass via Conduit 10 to hydrolysis Zone 26 wherein the alkoxides are converted to alcohols and aluminum compound by a hydrolyzing agent supplied via Conduit 16. The hydrolyzing agent will generally be an acid or water, depending upon the desired aluminum compound. When an acid is used, it generally is sulfuric yielding alum. Hydrochloric acid is sometimes used to produce aluminum chloride. When water is used, the aluminum compound will be alumina. In any case, the alcohols are removed via Conduit 11 and can be fractionated into individual alcohols if desired. The aluminum compound is removed -via Conduit 17. The reaction conditions in each zone are not given, since the individual steps are conventional. Pumps, fractionators, and the like are not shown, as these will be conventional and well known in the art. For example, the growth product can be fractionated and separately oxidized as can Stream 7 be oxidized separately from the growth product or fractions thereof. Thus, it can be readily recognized that the process of this invention prmgdes great flexibility in obtaining end products as desire To illustrate the flexibility of this invention, the following examples are given.

The process shown in the figure shows a general method of control on the distribution of aluminum alkyls and products derived from aluminum alkyls, over and above the control that currently exists in an alcohol process whereln the alcohol is produced from aluminum alkyls generally known as growth process when operated entrrely on ethylene and aluminum triethyl.

A generalized process description for this distribution control as follows (refer to the figure). The Olefins Generation Section 21 converts ethylene 1) to higher molecular weight alpha-olefins (2).

2 4 z)y H= Ha (I) This mixture of olefins (2) is fractionated in Olefins Fract onation Section 22 to produce olefin fractions (3) of either individual cuts, multiple carbon atoms cuts, or any other desirable combinations. At this point, selected alpha-olefin fractions can be made available for sale or for use as chemical intermediates (4). The desired olefins (5) for conversion to alcohols are then reacted with aluminum (12) and hydrogen (13) in the Aluminum Alkyls Generation Section 23 to form the corresponding aluminum alkyl compounds (6). The Aluminum Alkyls Generation Section 23 can be operated on individual olefin cuts, or olefin mixtures, to produce either pure aluminum alkyls or blends of aluminum alkyls, depending upon the composition of the olefin feed. The formation of the aluminum alkyls from the olefins could proceed by either the Aluminum Alkyl Hydrogenation/Alkylation Process, the Aluminum Triisobutyl/Displacement Process, or the Aluminum Diisobutyl Hydride/Alkylation Process.

Aluminum Alkyl Hydrogenation/Alkylation Process:

2 3 HAIR;

(b) all the aluminum alkyls (7) are fed directly to the oxidation reactor 25, or (c) a combination of (a) and (b).

In any case, the aluminum alkyls (7 and/or 9) are oxidized with air (15 in Oxidation Reactor 25 to form the corresponding aluminum alkoxides The aluminum alkoxides (10) are hydrolyzed with either water, acid, or base (16) in Hydrolysis Reactor 26 to form the desired alcohols and the byproduct aluminum compounds (17).

The composition diiferences between alcohols produced by this process and the conventional growth process are illustrated by the following examples. In these examples, the following definitions apply:

(1) Controlled alcohol distribution-The composition of the alcohols resulting from the process scheme under discussion. Basis is 100 pounds 618 alcohol, e.g., alcohols of 6 to 18 carbon atoms.

(2) Conventional alcohol distribution.The composition of the alcohols resulting from the aluminum triethylethylene growth reaction with an average of 3.7 ethylene additions per aluminum-carbon bond. Basis is 100 pounds 618 alcohol.

EXAMPLE NO. I

Olefins generation 21.-A process whereby ethylene is catalytically dimerized by aluminum alkyls to produce essentially l-butene.

Olefins fractionation 22.Produces essentially a pure stream (3) of l-butene. No. l-butene (4) is withdrawn from the process.

Aluminum alkyls generation 23.-Produces essentially pure aluminum tri-n-butyl (6).

Growth reactor 24.An average of 3.1 ethylene additions per aluminum-carbon bond.

EXAMPLE NO. II

Example IIA Olefins generation 21.-A process whereby ethylene is polymerized to higher molecular weight alpha-olefins by catalytic quantities of aluminum alkyls and further characterized in that the resulting distribution of the olefins follows an exponential function. Composition of stream (2) is as follows:

Olefin carbon No.: Weight percent Example IIA-l Olefins fractionation 22.The olefin stream (2) is fractionated into three cuts C -C C -C and C The 0 cut is removed from the process (4). The C -C and the C -C cuts are treated separately for conversion to aluminum alkyls. The following fractionation is made in 22:

Lbs. olefin/ lbs. 618 alcohols Aluminum alkyls generation 23.The above C -C and Cg-Clo olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactor 24.'Ihe C -C aluminum alkyls are reacted with ethylene such that an average of 2.6 moles ethylene is added per aluminum-carbon bond. The C -C aluminum alkyls are reacted with ethylene such that an average of 0.8 mole ethylene is added per aluminumcarbon bond.

ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional alcoh Olefins fractionation 22.The olefin stream (2) is fractionated into three cuts C -C C C and The C cut is removed from the process (4). The C -C and the (D -C cuts are treated separately for conversion to aluminum alkyls. The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols C4- 0 Cai0 Olefin Total cut out sales Oleign carbon number:

Total. 65. 92 33. 08 18. 87 13. 97

Aluminum alkyls generation 23.-The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactor 24.-The C -C aluminum alkyls are reacted with ethylene such that an average of 3.2 moles ethylene is added per aluminum-carbon bond. The C -C aluminum alkyls are reacted with ethylene such that an average of 1.8 moles ethylene is added per aluminumcarbon bond.

ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional a co co 01 distribution distribution Difierence Alcohol carbon number:

Example IIA-3 Olefins fractionation 22.The olefin stream (2) is fractionated into individual C C C C and C cuts. The C C and the C C cuts are recombined and converted separately to aluminum alkyls. The C 5 9 cut is re- 6 moved from the process (4). The following fractionation is made in 22:

Lbs. olefin/ lbs. 618 alcohols Cr-Ca C's-C10 Olefin Total cut out sales (5) Olefin carbon number:

Aluminum alkyls generation 23.-The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactors 24.An average of 2.6 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 1.6 moles ethylene is added per aluminum-carbon bond for the C -C alkyl.

ALCOHOL DISTRIBUTION (11) Lbs/106 lbs. 618 alcohol Controllled Conventional alco alcohol distribution distribution Difference Alcohol carbon number- Example IIA-4 Olefins fractionation 22.'Il1e olefin stream 2) is fractionated into individual C C C C and 0 cuts. The C -C and the C -C cuts are recombined and converted separately to aluminum alkyls. The (3 5+ cut is removed from the process (4). The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols C -C5 Cs-Cm Olefin Total cut out sales Olefin carbon number:

Aluminum alkyls generation 23.The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactors 24.An average of 3.2 moles ethylene is added per aluminum-carbon bond for the C 0 aluminum alkyl. An average of 1.6 moles ethylene is added per aluminum-carbon bond for the C -C alkyl.

ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional a1 1101 hol ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional co alco alcohol alcohol distribution distribution Difference distribution distribution Diflcrence Alcohol carbon number Total 108. 488 111. 970 3. 482 107. 395 111. 970 4. 575

Example IIB-Z Example IIB Olefins generation 21.A process whereby ethylene is polymerized to higher molecular weight alpha-Olefins by catalytic quantitie of aluminum alkyls and further characterized in that the resulting distribution of the olefins Olefins fractionation 22.The olefin stream 2) is fractionated into three cuts: C -C C -C and 0 The 0 cut is removed from the process (4). The C -C and the C -C cuts are treated separately for conversion to aluminum alkyls. The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols 4- 0 ar- 10 Olefin Total cut out sales Olefin carbon number:

Aluminum'alkyls' generation 23.-The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactor 24.The C -C aluminum alkyls are reacted with ethylene such that an average of 3.0 moles ethylene is added per aluminum-carbon bond. The C -C aluminum alkyls are reacted with ethylene such that an average of 0.6 mole ethylene is added per aluminumcarbon bond.

Olefins fractionation 22.The olefin stream (2) is fractionated into three cuts: C -C C -C and C The C cut is removed from the process (4). The C -C and the C -C cuts are treated separately for conversion to aluminum alkyls. The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols C4- 1: Cs-Cm Olefin Total cut cut sales (3) Olefin carbon number:

Aluminum alkyls generation 23.The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactors 24.The C -C aluminum alkyls are reacted with ethylene such that an average of 3.6 moles ethylene is added per aluminum-carbon bond. The C -C aluminum alkyls are reacted with ethylene such that an average of 1.0 mole ethylene is added per aluminumcarbon bond.

ALCOHOL DISTRIBUTION (11) Lbs/ lbs. 618 alcohol Controlled Conventional alcohol alcohol distribution distribution Difierence Alcohol carbon number:

EXAMPLE NO. III

Example IHA Olefins generation 21.A process whereby ethylene is polymerized to higher molecular weight alpha-Olefins by the continuous addition of ethylene to aluminum triethyl 75 and further characterized in that the resulting'distribution of the olefins follows a Poisson relationship. A possible distribution of stream (2) is as follows:

Olefin carbon No.: Weight percent 2 0.00 4 2.94

Example IIIA-l Olefins fractionation 22.-The olefin stream (2) is fractionated into three cuts: C -C C -C and The C cut is removed from the process (4). The C -C cut and the C -C cut are treated separately for conversion to aluminum alkyls. The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols C4-C0 (la-C10 Olefin Total cut out sales Oleizin carbon number:

Aluminum alkyls generation 23.The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactor 24.An. average of 2.6 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 0.8 mole ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl.

ALCOHOL DISTRIBUTION 11) Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol alcohol distribution distribution Difference 1 carbon number: 2 0. 898 2. 331 -1. 433 4- 1.163 6.707 5.544 6- 2. 950 13. 929 --10. 979 8.--- 17. 620 20. 278 2. 658 33. 340 21. 997 11. 343 12. 26. 015 18. 793 7. 222 14 13.000 13. 176 6. 176 16.-..-. 5. 191 7. 814 2. 623 18- 1. 880 4. 010 -2. 130 20-.. 0. 646 1.811 -1. 165 22+- 0. 293 1. 122 -0. 829

Example IIIA-2 The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohols C -C0 (Is-C1 Olefin Total cut out sales Olefin carbon number:

Total 139.53

Aluminum alkyls generation 23.-The above C -C and C C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth Reactor 24.An average of 2.8 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 1.8 moles ethylene is added per aluminum alkyl-carbon bond for the Cry-C10 aluminum alkyl.

ALCOHOL DISTRIBUTION 11 Lbs/100 lbs. 618 alcohol Controlled Conventional co 01 alcohol distribution distribution Difierence Alcohol carbon number:

Example KIA-3 Olefins fractionation 22.The olefin stream (2) is fractionated into a C -C cut, a C cut representing percent of the total C in the feed stream, a C -C cut containing the remaining C and a C +cut. The 0 cut is removed from the process (4). The C -C C and 0 C -C cuts are treated separately for conversion to aluminum alkyls.

The fOllowing fractionation is made in 22;

Lbs. olefin/ lbs. 618 alcohol C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The C -C and the C -C aluminum alkyl cuts are grown separately in Growth Reactors 24. The C aluminum alkyl cut (7) bypasses the Growth Reactors 24 to the Oxidation Reactor 25.

1 1 Growth Reactor 24.An average of 3.0 moles of ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 2.0 moles of ethylene is added per aluminum-carbon bond for the C -C cut.

ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol co distribution distribution Difierence Alcohol carbon number:

Example IIIA-4 Olefins fractionation 22.The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohol CrCu Ca (ls-C10 out out out Total (3) Olefin carbon number:

Controllled Conventional alco alcohol distribution distribution Difference Example IHA-5 Olefins fractionation 22.The olefin stream (2) is fractionated into a C -C cut, a C cut, a C cut, and a C cut. The C cut is removed from the process (4). The C -C C and C cuts are treated separately for conversion to aluminum alkyls.

The following fractionation is made in 22:

Lbs. olefin/ lbs. 618 alcohol C -C5 Olefin Total cut 0 out C cut sales Olefin carbon number:

Aluminum alkyls generation 23.The above C -C C and C cuts are converted to the corresponding aluminum alkyl. The C -C and the C aluminum alkyls are grown separately in Growth Reactors 24. The C aluminum alkyl cut (1) bypasses Growth Reactor 24 to the Oxidation Reactor 25.

Growth reactor 24.An average of 2.6 moles of ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 0.8 mole of ethylene is added per aluminum-carbon bond for the C aluminum alkyl.

Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol alcohol distribution distribution Difiercnce Alcohol carbon number:

Example IIIA-6 Olefins fractionation 22.The following fractionation is made in 22:

Lbs. olefin/100 lbs. 618 alcohol C4-C0 Olefin Total cut C cut C cut sales (3) Olefin carbon Aluminum alkyls generation 23.-The above C -C C and C cuts are converted to the corresponding aluminum alkyl. The C C and the C aluminum alkyls are grown separately in Growth Reactors 24. The C aluminum alkyl cut (7) bypasses growth Reactor 24 to the Oxidation Reactor 25.

Growth reactors 24.An average of 3.6 moles of ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 2.0 moles of ethylene is added per aluminum-carbon bond for the C aluminum alkyl. 7

' 41.015301. DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional ALCOHOL DISTRIBUTION (ll) Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol alcohol alcoh alcohol p I distribution distribution Difference distribution distribution Difierenoe Alcohol carbon number: Alcohol carbon number:

2 0.810 2.331 -1. 521 1. 039 2.331 -1. 292 4. 1. 135 0. 707 -5. 572 1. 881 0. 707 4. 826 6- 1. 964 13. 929 -11. 905 5. 235 13. 929 -3. 694 s- 30. 397 20.278 10. 119 20. 140 20. 27s -0. 132 a 10'. 10. 294 21. 997 -11. 703 30. 184 21. 997 8. 137 12-- 17.115 18. 793 -1. 678 10 23. 400 18.793 4. 007 14-. 13. 174 13. 170 4. 998 12. 802 13. 17s -0. 374 16.-- 13. 835 7. 314 0. 021 5. 838 7. 814 1.976 18-. 8.212 4.010 4.202 2, 85 4,010 -1.s25 20-- 4. 030 1. 811 2. 219 86 1, 811 -0, 925 22+ 2 667 1.122 1.545 0.420 1.122 -0. 702

Total. 108. 863 111. 970 8. 107 104. 217 111. 970 -7. 753

Example IIIB-2 Example IIIB Olefins fractionation 22.The olefin stream (2) is Olefins generation 21.A process whereby ethylene is gfictlonated Into. three cuts: CFCG and 012+ e C cut 15 removed from the process (4). The polymerized to higher molecular weight alpha-olefins by C C 6 cut and the C -C cut are treated separately for the connnuous addmon of ethylene to alummum methyl conversion to aluminum alk ls The followin fractionaand further characterized in that the resulting distribution tion is made in y g of'the olefins follows a Poisson relationship. A possible 25 distribution of stream (2) is as follows:

efi Ear-boll Weight Percent Lbs. olefin/100 lbs. 618 alcohols 2 C4-C5 01 C Olefin 4 12-01 0 Total cut cu sales 6 V 22.5 1 8 25-02 Olefin carbon number: 10 19.55 9 00 7 12 11.73 16:86 14 5.70 18-74 14. 64 16 '3; is 19 1s 0.

1.74 1. 74 20+ 00 0.61 0. 01 0.26 0. 26 Example HIE-1 40 74.93 25.86 33.33 15.67

Olefins fractionation 22.-The olefin stream (2) is fractionated into three cuts: C C C -C and C The C cut is removed from the process (4). The C -C cut and the C -C out are treated separated for conver- Aluminum alkyls generation 3.The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth reactors 24.--An average of 2.6 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 0.8 mole ethylene is added per aluminum-carbon bond for the C C aluminum alkyl.

Aluminum alkyls generation 23.The above C -C and C -C olefin cuts are converted to the corresponding aluminum alkyls. The aluminum alkyls are grown separately.

Growth Reactors 24.--An average of 3.0 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 1.8 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl.

ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol alcohol distribution distribution Dilference Example IIIC Olefins generation 21.A process whereby ethylene is polymerized to higher molecular weight alpha-olefins by the continuous addition of ethylene to aluminum triethyl and further characterized in that the resulting distribution of the olefins follows a Poisson relationship. A possible distribution of stream (2) is as follows:

Olefin carbon No.: Weight percent Olefins fractionation 22.The olefin stream (2) is fractionated and recombined as shown in the following table:

Lbs. olefin/100 lbs. 618 alcohol C4-C0 C-Cs-C10 Ca-Ciz-Cu cut cut (5) cut (5) Olefin sales (4) Total Olefin carbon ALCOHOL DISTRIBUTION (11) Lbs/100 lbs. 618 alcohol Controlled Conventional alcohol alcohol distribution distribution Difierenee Alcohol carbon number:

Example IIID Olefins generation 21.A process whereby ethylene is polymerized to higher molecular weight alpha-olefins by the continuous addition of ethylene to aluminum triethyl and further characterized in that the resulting distribution of the olefins follows a Poisson relationship. A distribution of stream (2) is as follows:

Olefin carbon No; Weight percent possible Olefins fractionation 22.The olefin stream (2) is fractionated into pure fractions and recombined as shown in the following table:

Lbs. olefin/ lbs. 618 alcohol C4-C6 Cs-OsCIO (Ir n- 14 cut (5) cut (5) Cut (5) Total Olefin sales (4) Olefin carbon mrnber:

Aluminum alkyl generation 23.The above C -C C C8C and C -C -C cuts are converted to the corresponding aluminum alkyls. The C -C and the C C -C aluminum alkyl cuts are grown separately in Growth Reactors 24. The C C C aluminum alkyl cut (7) bypasses the Growth Reactors 24 to Oxidation Reactor 25.

Growth reactors 24.An average of 3.5 moles ethylene is added per aluminum-carbon bond for the C -C aluminum alkyl. An average of 3.0 moles ethylene is added per aluminum-carbon bond for the c -c -c aluminum alkyl.

The preceding examples illustrate that the distribution control of the aluminum alkyls and alcohols derived from aluminum alkyls can be effected by any of, or combinations of, the following:

1) The process (A) whereby ethylene is converted to higher molecular weight alpha-olefins which results in various and different compositions of the olefin product (2) The fractionation of the olefin mixture (2) into various fractions which allows the formation of those desired aluminum alkyls for further processing (6) and/or allows various olefins to be removed from the process (4) for use as chemical intermediates and/or sales;

(3) The process of the aluminum alkyls derived from the alpha-olefins such that they may be (a) grown 17 with ethylene to higher molecular weight aluminum alkyls, (b) oxidized to the aluminum alkoxides Without further growth with ethylene, and (c) combinations of and (4) The addition of ethylene to the aluminum alkyl fractions in the Growth Reactors 24.

Having thus described the application, we claim:

1. A process for producing aluminum trialkyls of controlled chain length and distribution comprising:

(a) polymerizing ethylene to form a stream containing higher l-olefins;

(b) fractionating the stream of higher l-olefins and recovering at least one stream of l-olefins of preselected chain lengths for further processing;

(c) reacting the recovered l-olefins of preselected chain lengths with aluminum and hydrogen and forming aluminum trialkyls wherein the alkyl groups correspond to the preselected chain lengths; and

(d) reacting at least a portion of the thus formed aluminum trialkyls with ethylene in a growth reaction.

2. The process of claim 1 wherein the ethylene is polymerized to form l-olefins under pressure and temperature in the presence of aluminum triethyl as catalyst.

3. The process of claim 2 wherein the ethylene is dimerized to l-butene in step (a) and all of the aluminum trialkyls from step (c) are subjected to growth.

4. The process of claim 2 wherein the resulting distribution of the l-olefins from step (a) is characterized in that said distribution follows an exponential function.

5. A process for producing aluminum trialkyls of controlled chain length and distribution comprising:

(a) polymerizing ethylene to form a stream containing (b) fractionating the stream of higher l-olefins into a C -C cut, a C -C cut and a C cut;

(c) removing the cut from the process;

((1) reacting the l-olefins of the C -C cut and the Cg-Clo cut with aluminum and hydrogen and forming the corresponding aluminum trialkyls; and

(e) reacting at least a portion of the thus formed aluminum trialkyls with ethylene in a growth reaction.

6. The process of claim 5 wherein the l-olefins of the C -C cut and the C C out are separately reacted in step (d) to form corresponding aluminum trialkyls.

7. The process of claim 6 wherein the C -C trialkyl aluminum and the C -C trialkyl aluminum are grown separately.

8. The process of claim 7 wherein the C -C trialkyl aluminum have an average of 2.6 to 3.6 moles of ethylene added per aluminum carbon bond during growth and the C C trialkyl aluminum have an average of 0.6 to 2.0 moles of ethylene added per aluminum-carbon bond during growth.

9. A process for producing aluminum trialkyls of controlled chain length and distribution comprising:

(a) polymerizing ethylene to form a stream containing higher l-olefins;

(b) fractionating the stream of higher l-olefins and recovering a C -C 1-olefin cut, a C l-olefin cut, a C l-olefin cut and a 0 l-olefin cut; (c) removing the 0 l-olefins cut from the process; ((1) reacting the C C l-olefins cut, the C l-olefin cut and the C l-olefin cut with aluminum and hydrogen and forming the corresponding aluminum trialkyls; and

(e) reacting at least a portion of the thus formed aluminum trialkyls with ethylene in a growth reaction.

10. The process of claim 9 wherein each l-olefin cut is separately reacted to form the corresponding aluminum trialkyl and separately grown with ethylene.

11. The process according to claim 1 wherein the aluminum trialkyls from the growth reaction of step (d) are oxidized and then hydrolyzed.

12. The process of claim 5 wherein the aluminum trialkyls from the growth reaction of step (e) are oxidized and hydrolyzed.

13. The process of claim 9 wherein the C trialkyl aluminum formed in step (d) is oxidized and hydrolyzed without being subjected to the growth reaction of step (e).

14. The process of claim 13 wherein the remaining aluminum trialkyls formed in step (d) are subjected to the growth reaction of step (e) followed by oxidation and hydrolyzation.

References Cited UNITED STATES PATENTS 3,391,175 7/1968 Davis 260-448 A 3,077,490 2/1963 Fernald 260448 A 2,863,896 12/1958 Johnson 260448 A 3,423,444 1/1969 Atwood 260-448 A 3,384,651 5/1968 Davis 260-448 A 3,415,861 12/1968 Davis et al. 260-448 A 3,032,574 5/1962 Ziegler et al. 260-448 A 2,781,410 2/ 1957 Ziegler et al. 260-448 A HELEN M. S. SNEED, Primary Examiner US. Cl. X.R.

260-448 AD, 632 D 

